EP0408642B1 - Emulsion for water-in-oil emulsions - Google Patents
Emulsion for water-in-oil emulsions Download PDFInfo
- Publication number
- EP0408642B1 EP0408642B1 EP89904684A EP89904684A EP0408642B1 EP 0408642 B1 EP0408642 B1 EP 0408642B1 EP 89904684 A EP89904684 A EP 89904684A EP 89904684 A EP89904684 A EP 89904684A EP 0408642 B1 EP0408642 B1 EP 0408642B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lecithin
- water
- oil
- emulsions
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 155
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims abstract description 195
- 239000000787 lecithin Substances 0.000 claims abstract description 194
- 235000010445 lecithin Nutrition 0.000 claims abstract description 194
- 229940067606 lecithin Drugs 0.000 claims abstract description 192
- 239000012071 phase Substances 0.000 claims abstract description 75
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 32
- 239000008346 aqueous phase Substances 0.000 claims abstract description 19
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 20
- 229930006000 Sucrose Natural products 0.000 claims description 20
- 239000005720 sucrose Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229940083466 soybean lecithin Drugs 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims 1
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 238000004945 emulsification Methods 0.000 abstract description 10
- 239000003921 oil Substances 0.000 description 77
- 235000019198 oils Nutrition 0.000 description 59
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 9
- 210000002969 egg yolk Anatomy 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 208000016261 weight loss Diseases 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000003905 phosphatidylinositols Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 241000282849 Ruminantia Species 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 230000002587 anti-hemolytic effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000007903 gelatin capsule Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000002884 skin cream Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J7/00—Phosphatide compositions for foodstuffs, e.g. lecithin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/10—Phosphatides, e.g. lecithin
- C07F9/103—Extraction or purification by physical or chemical treatment of natural phosphatides; Preparation of compositions containing phosphatides of unknown structure
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/06—Protein or carboxylic compound containing
Definitions
- the present invention relates to emulsifiers for use in water-in-oil emulsions. More particularly, the present invention relates to the use of thermally altered lecithin as an emulsifier for water-in-oil emulsions and the stable water-in-oil emulsions prepared therewith.
- An emulsion can be defined as a dispersion of one immiscible liquid in another, stabilized by a third component, the emulsifying agent.
- Emulsion systems by their very nature are thermodynamically unstable. See, for example, Encyclopedia of Emulsion Technology , Vol. 2, pp. 159-170. This inherent problem of stability has often resulted in limited applications for many potentially useful emulsion systems. Stable, improved emulsion systems exhibiting good holding capacities are therefore ever in demand and on the forefront of development.
- Lecithin is well known, particularly as a surfactant and/or as an emulsifier. Lecithin is obtained from natural sources such as egg yolk, and plants such as soybean, maize, rapeseed, and the like where it is a by-product of vegetable oil refinement. The composition of commercial lecithin depends on the source, methods of preparation, and degree of purification, but in the most pure form it is comprised of mainly phosphatides. For example, granular soybean lecithin may contain principally phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol and the like.
- lecithin While lecithin is well-known as an emulsifier, it has been recognized as a somewhat inferior emulsifier, particularly for water-in-oil emulsions.
- the use of lecithin as an emulsifier is therefore generally most preferred in oil-in-water type emulsions, or with the lecithin, due to its being an inexpensive source, filling the role as a secondary emulsifier in the presence of a primary emulsifier.
- lecithin in emulsion explosives, wherein water-in-oil emulsions are often used, is well-documented.
- a number of publications exemplify this application. These include U.S. Patent Nos. 4,602,970, 4,507,161, 4,473,418, 4,308,081, 4,357,184, 4,555,278, British Patent Nos. 2,179,338 and 2,037,269; European Patent Application No. 0155800 and Australian Patent No. 10510/83.
- the lecithin employed is used as an emulsifier or surfactant, with the lecithin being normal lecithin such as soybean lecithin.
- 61-162148 discloses a method for preparing a creamy emulsified oil or fat composition containing a milk component by adding a modified lecithin thereto.
- the modified lecithin is selected from a phosphatidylcholine-rich fractionated lecithin, a phosphatidylethanolamine- and/or phosphatidylinositol-rich fractionated lecithin, a partially hydrolyzed lecithin in which part of the fatty acids are hydrolytically removed, an acetylated lecithin, and a lecithin modified by a combination of fractionation, hydrolysis and acetylation.
- the chemical modification can vary greatly, therefore, depending on the ultimate application of the lecithin.
- the heating of lecithin containing compositions in general, is known. Such heating generally takes place in the form of a sterilization step or a drying step.
- a few more specific instances of heating a lecithin containing composition include those described in U.S. Patent No. 4,670,247 and U.S. Patent No. 4,323,124.
- the first patent heats a composition containing lecithin to 180°C for about one minute, and then at lower temperatures for more extended periods of time, in order to crosslink various major materials within the composition.
- the second patent i.e., U.S. Patent No. 4,323,124, injects lecithin with steam into a bore hole so that the lecithin acts as a coating for the rock formation.
- the injected steam is at a temperature of from 260 to 302°C (500 to 575°F).
- Japanese Patent Application No. 60-214845 there is disclosed the preparation of a powder for use as an emulsifier in the food industry, primarily for use by confectioners and noodle manufacturers.
- the method involves heating a mixture of lecithin and starch at a temperature of from the gelatinization temperature of the starch to 140°C together with water to thereby form a lecithin-starch complex. This complex is then dried and powdered.
- U.S. Patent No. 4,157,404 discloses a specific lecithin, i.e., yolk lecithin.
- yolk lecithin is extremely susceptible to oxidation and therefore, when the yolk lecithin is heat treated at a temperature as high as 60°C or more under atmospheric pressure, the color of yolk lecithin changes from yellowish orange to brown through yellowish brown. Accordingly, the patent suggests that a heat treatment to remove solvent in order to obtain a yolk lecithin is undesirable.
- the suggested route, in order to avoid the degradation of the yolk lecithin, is a novel solvent extraction method.
- U.S. 2678320 discusses the reaction of sulfonated glyceride compounds with lecithin for the purpose of forming water soluble compounds which are useful as dispersing and emulsifying agents.
- U.S. 2299743 describes a reaction of lecithin (phosphatide) with an oil soluble peroxide or per-acid to improve the characteristics of some phosphatides.
- lecithin While the use of lecithin in various applications is well known, including applications as an emulsifier, and various modifications of lecithin to improve its use in these applications have been suggested, a truly effective yet simple emulsifier based upon lecithin, particularly for water-in-oil emulsions, has heretofore been unknown to the art. The recognition and existence of such a simple, effective and easily obtained emulsifier would certainly benefit the industry and encourage the use of emulsion systems, and particularly water-in-oil emulsion systems.
- Yet another object of the present invention is to provide such an emulsifier composition which is particularly effective in stabilizing water-in-oil emulsions.
- Still another object of the present invention is to provide a novel, stable water-in-oil emulsion which is comprised of such an emulsifier composition.
- Another object of the present invention is to provide a simple, novel process for preparing a stable water-in-oil emulsion.
- Yet another object of the present invention is to provide such a process for preparing a water-in-oil emulsion which exhibits good holding capacity with respect to the discontinuous aqueous phase.
- the thermally altered lecithin is prepared simply by heating lecithin. This heating is generally conducted under conditions of temperature, time and pressure to sufficiently alter the composition, e.g., the acetone precipitable content and fatty acid content, such that the emulsification properties of the lecithin are improved.
- the lecithin is heated at a temperature in the range of from about 100°C to about 250°C for a period of time ranging from about 15 to about 480 minutes, for it has been found that upon thermally altering lecithin in this manner, a unique and improved emulsifier for water-in-oil emulsions is obtained.
- a water-in-oil emulsion comprised of
- the thermally altered lecithin composition of the present invention which is useful as an emulsifier for water-in-oil emulsions is prepared by heating lecithin (unaltered) in either the granular or fluid form.
- the heating is preferably conducted at a temperature in the range of from 100°C to 250°C, more preferably at a temperature in the range of from 160°C to 200°C, and most preferably at a temperature in the range of from 175°C to 185°C.
- the duration of the heating is preferably for a length of time ranging from 15 to 480 minutes, and most preferably from 60 to 120 minutes.
- the heating of the lecithin can be conducted in an oil which is to be used as the continuous phase in a water-in-oil emulsion.
- a heat treatment has also been found to result in a thermally altered lecithin composition exhibiting the unique and beneficial emulsification properties of the present invention, while essentially eliminating a step in the preparation of the water-in-oil emulsion.
- the heating of lecithin in oil is preferably conducted at the same temperature and for the same time periods noted previously with respect to the direct heating of lecithin.
- the lecithin which can be used in the present invention can be lecithin derived from any plant, animal or microbial source. Suitable lecithin starting materials are commercially available, and include available soybean lecithin and yolk lecithin products. Lecithin derived from soybeans is most preferred. Examples of two soybean lecithin products that can be used successfully in the practice of this invention are CENTROLEX P (oil free phosphatides) granular lecithin (available from Central Soya Co., Inc., Fort Wayne, IN USA) and LECITHIN, PRACTICAL (available from Eastman Kodak Co., Rochester, NY USA). Another commercial lecithin source is Ross and Rowe, Inc., of Decatur, Illinois.
- a stable water-in-oil emulsion can be prepared using the thermally altered lecithin as the emulsifier.
- Such water-in-oil emulsions can be prepared by conventional means with the thermally altered lecithin being used as the emulsifier.
- a preferred process useful in the preparation of a water-in-oil emulsions in accordance with the present invention comprises the steps of
- step (i) the product of step (i) is allowed to cool to a temperature below 100°C before the aqueous phase is added thereto, e.g., to preferably about 80°C.
- the oil of the continuous phase can be any suitable oil such as a vegetable oil or a mineral oil, or mixtures thereof.
- a vegetable oil is soybean, sesame, safflower and cottonseed oils.
- Liquid paraffin is an example of a preferred mineral oil.
- the discontinuous agueous phase may consist of any dilute or concentrated aqueous solution involving a wide variety of organic or inorganic solutes, or a mixture of such substances.
- the final decision as to the content of the aqueous phase would depend, of course, on the intended application of the ultimate emulsion product.
- the oil content of the water-in-oil emulsion ranges from 1.5 to 6.0 weight percent, and most preferably from 1.8 to 5.5 weight percent, based upon the weight of the total emulsion composition.
- the amount of thermally altered lecithin employed as the sole or primary emulsifier preferably ranges from 0.05 to 2.5 weight percent, and most preferably from 0.08 to 2.2 weight percent.
- the discontinuous phase may comprise any percentage of the total emulsion composition. However, for best results, subject, of course, to the intended application of the emulsion product, the content of discontinuous phase should be just below the maximum discontinuous phase holding capacity of the emulsifier/oil.
- the resultant water-in-oil emulsions of the present invention exhibit excellent stability and holding capacity.
- the emulsions prepared with thermally altered lecithin in accordance with the present invention can hold as much as 183% more aqueous solution in the discontinuous phase than emulsions containing unaltered lecithin.
- such emulsions are stable for weeks compared to those prepared with unaltered lecithin, which show complete or partial deterioration within 24 hours.
- compositional changes that have been observed as resulting from the chemical reactions brought about by the heating of lecithin for a period of time and at a temperature sufficient to improve the emulsification properties as described herein, are 1) a modest loss of weight (probably due mainly to the loss of water), 2) a substantial reduction in the amount of acetone precipitable substances which is characterized by the almost complete loss of non-choline containing phosphatides and reduction in the phosphatidylcholine content, i.e., phosphatidylcholine being essentially the only phosphatide remaining in the thermally altered lecithin preparation, and 3) a change in the phosphatidylcholine-fatty acid composition whereby the relative proportions of diunsaturated fatty acids are greatly reduced, the saturated fatty acids are substantially increased, and the triunsaturated fatty acid is absent.
- the water-in-oil emulsions of the present invention prepared with thermally altered lecithin as described can be useful in a broad range of applications in areas where emulsions are currently employed, agriculture, pharmaceuticals, cosmetics, foods, etc. Applications in certain areas that heretofore have not envisioned a use for emulsions because of the lack of suitable emulsifiers that enable the preparation of sufficiently stable compositions with a broad range of properties might also be well served by the water-in-oil emulsions of the present invention.
- the following method was generally used in the preparation of an emulsion, unless otherwise specified:
- the emulsifier was dissolved in oil and heated to a temperature of from 70°C to 80°C.
- the discontinuous phase was heated to a similar temperature and poured slowly into the continuous phase while mixing vigorously with a kitchen food mixer. After all of the discontinuous phase had been added, the container of emulsion was removed from the heating apparatus and mixed further for 30 to 60 seconds.
- the continuous oil phase in the examples unless otherwise noted, was an oil available under the trademark KLEAROL from Witco, Sonneborn Division, New York, New York.
- the discontinuous aqueous phase in the examples was a 40 percent sucrose solution.
- the improved emulsification quality of thermally altered lecithin in accordance with the present invention as compared to unaltered lecithin was assessed in the examples by comparing two important properties of the respective emulsion products: (a) The discontinuous phase holding capacities (referred to hereafter as holding capacity) of the continuous phases containing the respective emulsifiers and (b) stability. Maintenance or changes in viscosity over time was also used as an indicator of stability or instability, respectively.
- holding capacity The discontinuous phase holding capacities of the continuous phases containing the respective emulsifiers
- stability Maintenance or changes in viscosity over time was also used as an indicator of stability or instability, respectively.
- Weight loss A known amount of lecithin was heated for a specified time and temperature, and the loss of weight was determined gravimetrically.
- Acetone precipitable content The amount of acetone precipitable material in the unaltered and thermally altered lecithin was determined by conventional methods, i.e., a small amount of a concentrated solution of lecithin was diluted with acetone. The insoluble material was collected by centrifugation, air-dried, and weighed.
- the phosphatide and neutral lipid composition of the unaltered and thermally altered lecithin was determined by thin-layer chromatography as described in Weete, J.D., M.S. Sancholle, and C. Montant. (1983). Biochim. Biophys. Acta 752:19-29.
- the individual phosphatides were separated using chloroform: acetone: methanol:acetic acid:water (30:40:10:10:5 by vol.) as the developing solvent, and the neutral lipids were separated using hexane:diethyl ether:acetic acid (79:20:4 by vol.).
- Fatty acid composition The fatty acid composition of the phosphatidylcholine was determined by gas liquid chromatography as described in Weete, J.D., M.S. Sancholle, and C. Montant. (1983). Biochim. Biophys. Acta 752:19-29.
- Example 1 the viscosity and holding capacity of emulsions prepared with thermally altered lecithin in accordance with the present invention were measured. These emulsions demonstrate the outstanding attributes which characterize the emulsions of the present invention. Various emulsions comprised of themally altered lecithin produced under different conditions of temperature and time were used. The measured viscosities and holding capacities, as well as the conditions of temperature and time used in preparing the thermally altered lecithin, are reported in Table 1 below.
- the holding capacity of the continuous phase prepared with thermally altered lecithin in accordance with the present invention as a function of time (30 to 480 minutes) at 180°C increased from 95 to 143 grams up to 90 minutes of heating, and essentially leveled off at 155 grams for 120 to 480 minutes of heating.
- the holding capacity of the emulsion prepared with thermally altered lecithin as a function of time at constant temperature was increased by 63%.
- TL emulsions were prepared with 6g continuous phase and a 40% sucrose solution as the discontinuous phase.
- emulsions were prepared as described except with 18 g less discontinuous phase than the holding capacity.
- b L Unaltered lecithin.
- L emulsions were prepared with 6 g continuous phase and a 40% sucrose solution as the discontinuous phase.
- emulsions were prepared with 12 g less than holding capacity.
- the viscosities of emulsions prepared with 6 grams of continuous phase containing thermally altered lecithin, and a 40% sucrose solution as the discontinuous phase increased progressively from 7000 mPa ⁇ s (cps) at 0.6/11.4 to 98000 mPa ⁇ s (cps) at 4.8/7.2, whereas the viscosities of corresponding emulsions prepared with unaltered lecithin increased only from 2000 mPa ⁇ s (cps) to 6000 mPa ⁇ s (cps).
- Example 3 emulsions were prepared with 12 grams of thermally altered lecithin in approximately the same emulsifier/oil ratios as employed in Example 2, except that a 10% sucrose solution was used rather than a 40% solution as the discontinuous phase.
- the viscosities of the emulsions increased proportionately with increasing emulsifier/oil ratio, doubling with each doubling of the emulsifier content.
- the viscosity of emulsions prepared with unaltered lecithin increased 2.4 times at an emulsifier/oil ratio of 4.5/7.5 over that at 2.5/9.5
- the range of viscosity values for the emulsions prepared with thermally altered lecithin was 10000 cps to 106000 cps (see Table 3).
- the holding capacity of a continuous phase containing thermally altered lecithin increased as a function of solute concentration in the discontinuous phase.
- the holding capacity increased 20% for emulsions with increasing sucrose concentration from 10% to 40%.
- the viscosities of the emulsions prepared with thermally altered lecithin increased with increasing solute concentration of the discontinuous phase.
- the viscosity of an emulsion prepared with a 10% sucrose solution was 4000 mPa ⁇ s (cps), and that prepared with 30% and 40% sucrose solutions was 6000 mPa ⁇ s (cps).
- the emulsion prepared with the 10% sucrose solution became relatively unstable over extended periods of time and temperatures
- the emulsion prepared with 30% for example, remained relatively stable for more than 14-days with respect to viscosity at 4°C, room temperature, and 65°C.
- lecithin was thermally altered in situ (while dissolved in oil) and the holding capacity of the continuous phase was determined as a function of lecithin originally placed into the oil prior to thermalization.
- Unaltered lecithin (1.25 g, 2.5 g, 3.75 g, and 5.0 g) was dissolved in 23.75 grams of oil and heated at 180°C for 60 minutes. Corresponding solutions with unaltered lecithin were used for comparison.
- phase separation refers to the non-random distribution of the particles (cells) containing the aqueous solution in the continuous phase, i.e., settling under the force of gravity.
- the emulsions are referred to as "broken" when the particles either coalesce forming larger particles or rupture whereby pockets of aqueous phase form within the emulsion and can be separated by centrifugation.
- a decrease in viscosity with time was also used as a measure of deterioration in stability. Stability as a function of pH was also determined.
- Emulsions prepared with unaltered lecithin at various emulsifier/oil concentrations were generally unstable and exhibited complete or partial phase separation and breakdown within 24 hours of preparation.
- the best emulsion prepared with unaltered lecithin contained 4.5 grams emulsifier and 7.5 grams of oil. This creamy-yellow emulsion was stable for 48 hours but thereafter began to show phase separation and breakdown. Upon centrifugation of this emulsion at 2000 rpm for 10 minutes soon after preparation, some water settled to the bottom of the tube and oil rose to the top.
- Emulsions were prepared using 6 grams of thermally altered lecithin/oil (0.3/5.7) and a 40% sucrose solution adjusted to the desired pH (1 to 11) with either HCl or NaOH as the discontinuous phase. Various properties of the emulsions were then determined, which are reported in Table 7 below.
- Emulsions were prepared using varying amounts of continuous phase, discontinuous phase and emulsifier/oil ratios. Both thermally altered lecithin and unaltered lecithin were employed as emulsifiers, as indicated in Table 8 below. The viscosity and permeability of the various emulsions were determined. The results are reported in Table 8 below.
- permeability in the context of the present illustration is used to indicate the loss of water from the emulsion as a function of time under desiccating conditions (a sealed container with CaCl2 as the dessicant).
- Example 9 The four emulsions prepared in Example 9 were tested for viscosity after being subjected to different temperatures. Viscosity measurements were made after 48 hours and after 14 days. The results are reported in Table 10 below. The results indicate that the emulsions remained remarkably stable with respect to viscosity for more than 14 days, regardless of temperature. TABLE 10 Effects of temperatures on the viscosity of emulsions prepared with thermally altered lecithin.
- an emulsion was prepared with thermally altered lecithin/oil (0.3 g/5.7 g) as the continuous phase and 10% NaCl as the discontinuous phase.
- the holding capacity of this continuous phase was 113 grams, and the viscosity of such an emulsion prepared with 101.4 grams of 10% NaCl solution was 13,000 mPa ⁇ s (cps).
- Acetone precipitable substances comprised about 95% percent of the granular lecithin (Centrolex P, Central Soya, Decatur, Indiana) used. Thermalization up to 200°C resulted in a 68% reduction in acetone precipitable substances, and the content of these substances remained relatively constant at 31 to 34% of the total weight of the thermally altered lecithin thereafter up to 250°C. Between 30 and 60 minutes were required to achieve maximum reduction of the acetone precipitable substances when the lecithin was heated at 180°C, and the content of these substances remained relatively constant thereafter up to 480 minutes exposure to this temperature.
- the neutral fraction of the thermally altered lecithin contained mainly triacylglycerols, free fatty acids, and two classes of substances unidentified.
- the fatty acid composition of phosphatidylcholine isolated from thermally altered lecithin and unaltered lecithin was compared. It was found that there was an overall increase in the degree of saturation associated with the thermally altered product as shown by a doubling of the relative contents of palmitic and stearic acids, and to the elimination of the most unsaturated component of the phosphatidylcholine molecule, linolenic acid, and reduction by half of linoleic acid. These results are shown in Table 16 below. TABLE 16 Fatty acid composition of phosphatidylcholine from lecithin before and after thermalization.
- An emulsion was prepared with a thermally altered lecithin/oil ratio of 3 g/5 g as the continuous phase, and 188.2 grams of an 80% ammonium nitrate solution containing 2 grams urea and 1.2 grams triethanolamine as the discontinuous phase.
- the objective of this example was to demonstrate that an aqueous solution of a very high salt concentration can be effectively emulsified using thermally altered lecithin as the emulsifier into a highly stable emulsion.
- the resulting emulsion was found very stable in that there was no phase separation and no crystallization of the ammonium nitrate within the supersaturated discontinuous phase for over three months after preparation.
- the emulsion prepared had a viscosity of 56,000 mPa ⁇ s (cps).
- a comparative emulsion was prepared with unaltered lecithin in an emulsifier/oil ratio of 4.5/7.5.
- the emulsion had a viscosity of 15,000 mPa ⁇ s (cps).
- the viscosity of this emulsion dropped with time at room temperature to 9,000 mPa ⁇ s (cps) at 48 hours, 4,000 mPa ⁇ s (cps) at 72 hours and 3,000 mPa ⁇ s (cps) at 96 hours, which indicated a progressive deterioration with time.
- Emulsions were prepared using a constant (0.3 g) amount of thermally altered lecithin and varying oil (Klearol) contents, and 40% sucrose as the discontinuous phase, to determine the effect of oil content on emulsion formation and the stability of such emulsions.
- the results are reported in Table 17 below.
- the holding capacity of the continuous phases increased progressively with increasing oil content from 150 g at 6 g of oil to 360 g at 20 g of oil which is a 140% increase in holding capacity.
- the emulsion having the lowest oil content had the highest viscosity at 6000 mPa ⁇ s (cps), and that of the emulsion containing 9 g oil was 4000 mPa ⁇ s (cps).
- the viscosity of emulsions containing 12 to 20 g of oil was 2000 mPa ⁇ s (cps).
- the emulsion containing only 6 g of oil lost the greatest amount of water 4 days after preparation but 2 days in the dessiccating environment, whereas water loss from the other emulsions was relatively constant.
- the emulsions containing 6 and 9 g of oil remained stable for at least 18 days after preparation, but the ones with higher oil contents showed phase separation after 6 days and had decomposed after 14 days.
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Abstract
Description
- The present invention relates to emulsifiers for use in water-in-oil emulsions. More particularly, the present invention relates to the use of thermally altered lecithin as an emulsifier for water-in-oil emulsions and the stable water-in-oil emulsions prepared therewith.
- An emulsion can be defined as a dispersion of one immiscible liquid in another, stabilized by a third component, the emulsifying agent. Emulsion systems, however, by their very nature are thermodynamically unstable. See, for example, Encyclopedia of Emulsion Technology, Vol. 2, pp. 159-170. This inherent problem of stability has often resulted in limited applications for many potentially useful emulsion systems. Stable, improved emulsion systems exhibiting good holding capacities are therefore ever in demand and on the forefront of development.
- Lecithin is well known, particularly as a surfactant and/or as an emulsifier. Lecithin is obtained from natural sources such as egg yolk, and plants such as soybean, maize, rapeseed, and the like where it is a by-product of vegetable oil refinement. The composition of commercial lecithin depends on the source, methods of preparation, and degree of purification, but in the most pure form it is comprised of mainly phosphatides. For example, granular soybean lecithin may contain principally phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol and the like.
- The literature is replete with references to the use of lecithin in various applications. For example, the applications include the use of lecithin in:
- foodstuffs such as mayonnaise, sponge cake, confectioneries such as whipping cream and chocolate, dried dairy products such as powdered creams for coffee, and steam cooked noodles;
- cosmetics such as skin creams, shampoos and hair dressing agents;
- emulsions for producing doughs or batter for bakery products;
- pharmaceutical preparations, including acne preparations, antihemolytic emulsions, compositions for the treatment of bloat in ruminants, and carcinostatic drug compositions;
- non-stick cooking compositions used for coating cookware;
- vehicles for hard and soft gelatin capsules;
- polymer compositions, including polyester molding compositions, water soluble polyvinyl acetate films and a resin dispersion of an electrophotographer, as well as an asphalt emulsion for use in pavements;
- fungicide and pesticide dispersions;
- hydraulic fluids; and,
- emulsion explosive compositions.
- While lecithin is well-known as an emulsifier, it has been recognized as a somewhat inferior emulsifier, particularly for water-in-oil emulsions. The use of lecithin as an emulsifier is therefore generally most preferred in oil-in-water type emulsions, or with the lecithin, due to its being an inexpensive source, filling the role as a secondary emulsifier in the presence of a primary emulsifier.
- For example, the use of lecithin in emulsion explosives, wherein water-in-oil emulsions are often used, is well-documented. A number of publications exemplify this application. These include U.S. Patent Nos. 4,602,970, 4,507,161, 4,473,418, 4,308,081, 4,357,184, 4,555,278, British Patent Nos. 2,179,338 and 2,037,269; European Patent Application No. 0155800 and Australian Patent No. 10510/83. In all of these publications, the lecithin employed is used as an emulsifier or surfactant, with the lecithin being normal lecithin such as soybean lecithin. Some of these publications, however, do suggest that the lecithin should be used as a secondary emulsifier, and/or that lecithin is basically an inferior emulsifier.
- The chemical modification of lecithin is known in the art as one manner in which to improve the lecithin for many different applications. U.S. Patent No. 4,479,977, for example, discusses the acylation of lecithins to provide a clear, heat resistant lecithin useful as a release agent. Hydrolyzed lecithins are disclosed as being useful surfactants or emulsifiers. U.S. Patent No. 4,547,387 discloses a rearrangement reaction product of a lecithin to form a better anti-spattering agent for margarine. Japanese Patent Application No. 61-162148 discloses a method for preparing a creamy emulsified oil or fat composition containing a milk component by adding a modified lecithin thereto. The modified lecithin is selected from a phosphatidylcholine-rich fractionated lecithin, a phosphatidylethanolamine- and/or phosphatidylinositol-rich fractionated lecithin, a partially hydrolyzed lecithin in which part of the fatty acids are hydrolytically removed, an acetylated lecithin, and a lecithin modified by a combination of fractionation, hydrolysis and acetylation. The chemical modification can vary greatly, therefore, depending on the ultimate application of the lecithin.
- The heating of lecithin containing compositions, in general, is known. Such heating generally takes place in the form of a sterilization step or a drying step.
- A few more specific instances of heating a lecithin containing composition include those described in U.S. Patent No. 4,670,247 and U.S. Patent No. 4,323,124. The first patent heats a composition containing lecithin to 180°C for about one minute, and then at lower temperatures for more extended periods of time, in order to crosslink various major materials within the composition. The second patent, i.e., U.S. Patent No. 4,323,124, injects lecithin with steam into a bore hole so that the lecithin acts as a coating for the rock formation. The injected steam is at a temperature of from 260 to 302°C (500 to 575°F).
- In Japanese Patent Application No. 60-214845, there is disclosed the preparation of a powder for use as an emulsifier in the food industry, primarily for use by confectioners and noodle manufacturers. The method involves heating a mixture of lecithin and starch at a temperature of from the gelatinization temperature of the starch to 140°C together with water to thereby form a lecithin-starch complex. This complex is then dried and powdered.
- The problems encountered upon subjecting lecithin to heat are also recognized in the art, however, and solutions to avoid either using heat or to improve the chemical integrity of the lecithin at higher temperatures have been suggested.
- For example, in U.S. Patent No. 4,479,977, it is disclosed that the loss of chemical integrity by lecithin during heating is well documented. Lecithin is known to darken and give off odors upon heating. These changes are traced to a number of complex reactions between or within the phosphatide molecules. The object Of the patent, therefore, is to avoid the decomposition of lecithin and improve its "chemical integrity" at higher temperatures. The solution suggested in the patent is acylating the lecithin in order to make it a heat resistant release agent.
- U.S. Patent No. 4,157,404 discloses a specific lecithin, i.e., yolk lecithin. The patent discloses that yolk lecithin is extremely susceptible to oxidation and therefore, when the yolk lecithin is heat treated at a temperature as high as 60°C or more under atmospheric pressure, the color of yolk lecithin changes from yellowish orange to brown through yellowish brown. Accordingly, the patent suggests that a heat treatment to remove solvent in order to obtain a yolk lecithin is undesirable. The suggested route, in order to avoid the degradation of the yolk lecithin, is a novel solvent extraction method.
- Thus, the two foregoing patents both discuss methods designed to avoid any heat treatment of lecithin. The suggestion is that upon heat treating lecithin, the results are bad and the resulting products are useless and/or undesirable.
- U.S. 2678320 discusses the reaction of sulfonated glyceride compounds with lecithin for the purpose of forming water soluble compounds which are useful as dispersing and emulsifying agents.
- U.S. 2299743 describes a reaction of lecithin (phosphatide) with an oil soluble peroxide or per-acid to improve the characteristics of some phosphatides.
- While the use of lecithin in various applications is well known, including applications as an emulsifier, and various modifications of lecithin to improve its use in these applications have been suggested, a truly effective yet simple emulsifier based upon lecithin, particularly for water-in-oil emulsions, has heretofore been unknown to the art. The recognition and existence of such a simple, effective and easily obtained emulsifier would certainly benefit the industry and encourage the use of emulsion systems, and particularly water-in-oil emulsion systems.
- Accordingly, it is an object of the present invention to provide a simple and easily prepared emulsifier composition which exhibits improved emulsification characteristics.
- Yet another object of the present invention is to provide such an emulsifier composition which is particularly effective in stabilizing water-in-oil emulsions.
- Still another object of the present invention is to provide a novel, stable water-in-oil emulsion which is comprised of such an emulsifier composition.
- Another object of the present invention is to provide a simple, novel process for preparing a stable water-in-oil emulsion.
- Yet another object of the present invention is to provide such a process for preparing a water-in-oil emulsion which exhibits good holding capacity with respect to the discontinuous aqueous phase.
- These and other objects, as well as the scope, nature and utilization of the invention, will be apparent to those skilled in the art from the following description and the appended claims.
- The foregoing objectives are realized by the present invention in providing a thermally altered lecithin composition which is useful for water-in-oil emulsions. Basically, the thermally altered lecithin is prepared simply by heating lecithin. This heating is generally conducted under conditions of temperature, time and pressure to sufficiently alter the composition, e.g., the acetone precipitable content and fatty acid content, such that the emulsification properties of the lecithin are improved. In a preferred embodiment, the lecithin is heated at a temperature in the range of from about 100°C to about 250°C for a period of time ranging from about 15 to about 480 minutes, for it has been found that upon thermally altering lecithin in this manner, a unique and improved emulsifier for water-in-oil emulsions is obtained.
- Accordingly, in another preferred embodiment of the present invention, there is provided a water-in-oil emulsion comprised of
- (i) a continuous oil phase,
- (ii) a discontinuous aqueous phase, and
- (iii) an emulsion stabilizing amount of a thermally altered lecithin composition which has been prepared by heating lecithin at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes.
- In another preferred embodiment of the present invention there is provided a process for preparing such a water-in-oil emulsion. The process can comprise the steps of
- (i) heating lecithin at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes,
- (ii) mixing the product of (i) with an oil, and
- (iii) adding to the product of (ii) an aqueous phase with agitation to thereby yield a water-in-oil emulsion; or,
- (i) heating lecithin in an oil at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes, and
- (ii) adding to the product of (i) an aqueous phase with agitation to thereby yield a water-in-oil emulsion.
- These processes have been found to be simple yet effective in producing a stable water-in-oil emulsion.
- The thermally altered lecithin composition of the present invention which is useful as an emulsifier for water-in-oil emulsions is prepared by heating lecithin (unaltered) in either the granular or fluid form. The heating is preferably conducted at a temperature in the range of from 100°C to 250°C, more preferably at a temperature in the range of from 160°C to 200°C, and most preferably at a temperature in the range of from 175°C to 185°C. The duration of the heating is preferably for a length of time ranging from 15 to 480 minutes, and most preferably from 60 to 120 minutes. It has been found that such a heat treatment results in thermally induced chemical modifications of the lecithin, which manifest themselves in the acetone precipitable content and fatty acid content of the thermally altered lecithin, to provide a composition with significantly improved emulsification qualities.
- In an alternative embodiment, the heating of the lecithin can be conducted in an oil which is to be used as the continuous phase in a water-in-oil emulsion. Such a heat treatment has also been found to result in a thermally altered lecithin composition exhibiting the unique and beneficial emulsification properties of the present invention, while essentially eliminating a step in the preparation of the water-in-oil emulsion. The heating of lecithin in oil is preferably conducted at the same temperature and for the same time periods noted previously with respect to the direct heating of lecithin.
- It should also be noted that the preferred ranges of time and temperature noted previously may change somewhat based upon the pressure employed in the heating environment. The foregoing ranges are contemplated for use at atmospheric pressure. As the pressure changes, so may the temperature and time requirements of the heating step. The necessary changes, however, should become readily apparent to the skilled artisan.
- The lecithin which can be used in the present invention can be lecithin derived from any plant, animal or microbial source. Suitable lecithin starting materials are commercially available, and include available soybean lecithin and yolk lecithin products. Lecithin derived from soybeans is most preferred. Examples of two soybean lecithin products that can be used successfully in the practice of this invention are CENTROLEX P (oil free phosphatides) granular lecithin (available from Central Soya Co., Inc., Fort Wayne, IN USA) and LECITHIN, PRACTICAL (available from Eastman Kodak Co., Rochester, NY USA). Another commercial lecithin source is Ross and Rowe, Inc., of Decatur, Illinois.
- Once the thermally altered lecithin has been prepared, a stable water-in-oil emulsion can be prepared using the thermally altered lecithin as the emulsifier. Such water-in-oil emulsions can be prepared by conventional means with the thermally altered lecithin being used as the emulsifier. However, a preferred process useful in the preparation of a water-in-oil emulsions in accordance with the present invention comprises the steps of
- (i) heating lecithin at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes,
- (ii) mixing the product of (i) with an oil, and
- (iii) adding to the product of (ii) an aqueous phase with agitation to thereby yield a water-in-oil emulsion.
- (i) heating lecithin in an oil at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes, and
- (ii) adding to the product of (i) an aqueous phase with agitation to thereby yield a water-in-oil emulsion.
- In a most preferred embodiment with respect to the latter process, the product of step (i) is allowed to cool to a temperature below 100°C before the aqueous phase is added thereto, e.g., to preferably about 80°C.
- In preparing the water-in-oil emulsions of the present invention, the oil of the continuous phase can be any suitable oil such as a vegetable oil or a mineral oil, or mixtures thereof. Among the preferred vegetable oils is soybean, sesame, safflower and cottonseed oils. Liquid paraffin is an example of a preferred mineral oil.
- The discontinuous agueous phase may consist of any dilute or concentrated aqueous solution involving a wide variety of organic or inorganic solutes, or a mixture of such substances. The final decision as to the content of the aqueous phase would depend, of course, on the intended application of the ultimate emulsion product.
- It is preferred that the oil content of the water-in-oil emulsion ranges from 1.5 to 6.0 weight percent, and most preferably from 1.8 to 5.5 weight percent, based upon the weight of the total emulsion composition. The amount of thermally altered lecithin employed as the sole or primary emulsifier preferably ranges from 0.05 to 2.5 weight percent, and most preferably from 0.08 to 2.2 weight percent. The discontinuous phase may comprise any percentage of the total emulsion composition. However, for best results, subject, of course, to the intended application of the emulsion product, the content of discontinuous phase should be just below the maximum discontinuous phase holding capacity of the emulsifier/oil.
- The resultant water-in-oil emulsions of the present invention exhibit excellent stability and holding capacity. In essence, the emulsions prepared with thermally altered lecithin in accordance with the present invention can hold as much as 183% more aqueous solution in the discontinuous phase than emulsions containing unaltered lecithin. Furthermore, such emulsions are stable for weeks compared to those prepared with unaltered lecithin, which show complete or partial deterioration within 24 hours.
- In theory, it is believed that the thermalization of the lecithin brings about a series of chemical reactions that result in the optimization of the quality and quantity of specific lipophilic substances in a complex mixture such that, under the conditions favorable for emulsification, the organization of molecules into thermodynamically stable interfacial layers is maximized. As a result, extremely beneficial emulsification properties are exhibited in particularly, water-in-oil emulsions.
- Among the compositional changes that have been observed as resulting from the chemical reactions brought about by the heating of lecithin for a period of time and at a temperature sufficient to improve the emulsification properties as described herein, are 1) a modest loss of weight (probably due mainly to the loss of water), 2) a substantial reduction in the amount of acetone precipitable substances which is characterized by the almost complete loss of non-choline containing phosphatides and reduction in the phosphatidylcholine content, i.e., phosphatidylcholine being essentially the only phosphatide remaining in the thermally altered lecithin preparation, and 3) a change in the phosphatidylcholine-fatty acid composition whereby the relative proportions of diunsaturated fatty acids are greatly reduced, the saturated fatty acids are substantially increased, and the triunsaturated fatty acid is absent. Among the characterizable new products formed during the thermalization of lecithin are triacylglycerols, free fatty acids and two types of condensable and esterifiable substances. Also observed is an uncharacterized dark brown substance(s) that is believed to be mainly a phosphatide reaction product(s).
- The water-in-oil emulsions of the present invention prepared with thermally altered lecithin as described can be useful in a broad range of applications in areas where emulsions are currently employed, agriculture, pharmaceuticals, cosmetics, foods, etc. Applications in certain areas that heretofore have not envisioned a use for emulsions because of the lack of suitable emulsifiers that enable the preparation of sufficiently stable compositions with a broad range of properties might also be well served by the water-in-oil emulsions of the present invention.
- The following examples are given as specific illustrations of the claimed invention and the benefits thereof. All parts and percentages in the example and the remainder of the specification are by weight unless otherwise specified.
- In the examples, the following method was generally used in the preparation of an emulsion, unless otherwise specified:
The emulsifier was dissolved in oil and heated to a temperature of from 70°C to 80°C. The discontinuous phase was heated to a similar temperature and poured slowly into the continuous phase while mixing vigorously with a kitchen food mixer. After all of the discontinuous phase had been added, the container of emulsion was removed from the heating apparatus and mixed further for 30 to 60 seconds. The continuous oil phase in the examples, unless otherwise noted, was an oil available under the trademark KLEAROL from Witco, Sonneborn Division, New York, New York. The discontinuous aqueous phase in the examples, unless otherwise noted, was a 40 percent sucrose solution. - The improved emulsification quality of thermally altered lecithin in accordance with the present invention as compared to unaltered lecithin was assessed in the examples by comparing two important properties of the respective emulsion products: (a) The discontinuous phase holding capacities (referred to hereafter as holding capacity) of the continuous phases containing the respective emulsifiers and (b) stability. Maintenance or changes in viscosity over time was also used as an indicator of stability or instability, respectively.
- When the weight loss, acetone precipitable content, fatty acid content or phosphatide content was determined in the examples, the following methods were employed:
Weight loss - A known amount of lecithin was heated for a specified time and temperature, and the loss of weight was determined gravimetrically. - Acetone precipitable content - The amount of acetone precipitable material in the unaltered and thermally altered lecithin was determined by conventional methods, i.e., a small amount of a concentrated solution of lecithin was diluted with acetone. The insoluble material was collected by centrifugation, air-dried, and weighed.
- The phosphatide and neutral lipid composition of the unaltered and thermally altered lecithin was determined by thin-layer chromatography as described in Weete, J.D., M.S. Sancholle, and C. Montant. (1983). Biochim. Biophys. Acta 752:19-29. The individual phosphatides were separated using chloroform: acetone: methanol:acetic acid:water (30:40:10:10:5 by vol.) as the developing solvent, and the neutral lipids were separated using hexane:diethyl ether:acetic acid (79:20:4 by vol.).
- Fatty acid composition - The fatty acid composition of the phosphatidylcholine was determined by gas liquid chromatography as described in Weete, J.D., M.S. Sancholle, and C. Montant. (1983). Biochim. Biophys. Acta 752:19-29.
- In Example 1, the viscosity and holding capacity of emulsions prepared with thermally altered lecithin in accordance with the present invention were measured. These emulsions demonstrate the outstanding attributes which characterize the emulsions of the present invention. Various emulsions comprised of themally altered lecithin produced under different conditions of temperature and time were used. The measured viscosities and holding capacities, as well as the conditions of temperature and time used in preparing the thermally altered lecithin, are reported in Table 1 below.
- Upon a review of the results, it can be seen that the holding capacity of the continuous phase prepared with thermally altered lecithin in accordance with the present invention as a function of time (30 to 480 minutes) at 180°C increased from 95 to 143 grams up to 90 minutes of heating, and essentially leveled off at 155 grams for 120 to 480 minutes of heating. Overall, the holding capacity of the emulsion prepared with thermally altered lecithin as a function of time at constant temperature was increased by 63%.
- The holding capacity of the continuous phase prepared with lecithin exposed to various temperatures (100 to 250°C) for 60 minutes remained constant at 101 grams of discontinuous phase up to 175°C and increased thereafter to 179 grams at 250°C. Overall, the holding capacity of emulsions prepared with thermally altered lecithin as a function of increasing temperature at constant time was increased by 78%.
- To illustrate the significant improvement in the emulsification quality of lecithin through thermalization in accordance with the present invention, various emulsions were prepared with 6 grams of a continuous phase having different emulsifier/oil ratios using either thermally altered lecithin or unaltered lecithin. The holding capacities and viscosities of the emulsions were then measured. Table 2, below, reports the results.
TABLE 2 Comparison of emulsions prepared with thermally altered lecithin and unaltered lecithin as a function of emulsifier/oil ratio.a , b Emulsifier/oil ratio Discontinuous phase Holding capacity (g) TL>L (%) Viscosity mPa·s (cps) TL L TL L 0.6/11.4 (TL and L) 137 95 44 7000 2000 1.2/10.8 (TL) 180 - 100 30000 - 1.25/10.75 (L) - 90 - 4000 2.4/9.6 (TL) 215 - 139 53000 - 2.5/9.5 (L) - 90 - 6000 4.0/8.0 (TL) 221 - - - - 4.8/7.2 (TL) 221 - 183 98000 - 4.5/7.5 (L) - 78 - 6000 a TL = Thermally altered lecithin. TL emulsions were prepared with 6g continuous phase and a 40% sucrose solution as the discontinuous phase. For viscosity measurements, emulsions were prepared as described except with 18 g less discontinuous phase than the holding capacity. b L = Unaltered lecithin. L emulsions were prepared with 6 g continuous phase and a 40% sucrose solution as the discontinuous phase. For viscosity measurements, emulsions were prepared with 12 g less than holding capacity. - In Table 2, it can be seen that the holding capacities of emulsions prepared with unaltered lecithin were relatively constant with increasing emulsifier content in the continuous phase at 90 to 95 grams for emulsifier/oil ratios of 0.6/11.4, 1.25/10.75, and 2.5/9.5, and decreased to 78 grams for a ratio of 4.5/7.5. On the other hand, the holding capacities of emulsions prepared with thermally altered lecithin in accordance with the invention increased progressively with increasing emulsifier/oil ratio from 137 to 221 grams. The overall improvement of holding capacity with respect to emulsions prepared with unaltered lecithin was from 44% to 183%.
- With respect to viscosity, the viscosities of emulsions prepared with 6 grams of continuous phase containing thermally altered lecithin, and a 40% sucrose solution as the discontinuous phase, increased progressively from 7000 mPa·s (cps) at 0.6/11.4 to 98000 mPa·s (cps) at 4.8/7.2, whereas the viscosities of corresponding emulsions prepared with unaltered lecithin increased only from 2000 mPa·s (cps) to 6000 mPa·s (cps).
- There was an overall 14-fold increase in viscosity over the emulsifier/oil ratio range tested for emulsions containing thermally altered lecithin as opposed to only a threefold increase for emulsions prepared with unaltered lecithin.
- In Example 3, emulsions were prepared with 12 grams of thermally altered lecithin in approximately the same emulsifier/oil ratios as employed in Example 2, except that a 10% sucrose solution was used rather than a 40% solution as the discontinuous phase.
- As can be seen from Table 3 below, increases in the holding capacity of the emulsions containing thermally altered lecithin vis-a-vis those containing unaltered lecithin were observed.
- With respect to viscosity, the viscosities of the emulsions increased proportionately with increasing emulsifier/oil ratio, doubling with each doubling of the emulsifier content. The viscosity of emulsions prepared with unaltered lecithin increased 2.4 times at an emulsifier/oil ratio of 4.5/7.5 over that at 2.5/9.5 There was an overall 10.6-fold increase in emulsion viscosity over the emulsifier/oil ratio range tested. The range of viscosity values for the emulsions prepared with thermally altered lecithin was 10000 cps to 106000 cps (see Table 3). The viscosities of similarly prepared emulsions with unaltered lecithin as the emulsifier ranged only from 2000 mPa·s (cps) to 14000 mPa·s (cps).
TABLE 3 Comparison of emulsions prepared with thermally altered lecithin and unaltered lecithin as a function of emulsifier/oil ratioa Emulsifier/oil ratio Discontinuous Phase Holding Capacity (g) % Improvement Viscosity mPa·s (cps) TL L (TL>L) TL L 0.5/11.5 (TL) 202 - 25 10000 - 0.6/11.4 ( L) - 161 - 2000 1.0/11.0 (TL) 280 - 74 22000 - 1.25/10.75 (L) - 161 - 3000 2.0/10 (TL) 334 - 107 44000 - 2.5/9.5 (L) - 161 - 5000 4.0/8.0 (TL) 406 - 184 106000 - 4.5/7.5 (L) - 143 - 14000 6.0/6.0 (TL) 286 - - - - a Prepared using 12 g continuous phase and 10% sucrose at the discontinuous phase at 12 g less than holding capacity. - In this example, the holding capacity and viscosity of emulsions prepared in accordance with the present invention were monitored as a function of sucrose concentration in the discontinuous phase. The results are reported in Table 4 below.
- From Table 4, it can be seen that the holding capacity of a continuous phase containing thermally altered lecithin increased as a function of solute concentration in the discontinuous phase. For example, the holding capacity increased 20% for emulsions with increasing sucrose concentration from 10% to 40%.
- The viscosities of the emulsions prepared with thermally altered lecithin increased with increasing solute concentration of the discontinuous phase. For example, the viscosity of an emulsion prepared with a 10% sucrose solution was 4000 mPa·s (cps), and that prepared with 30% and 40% sucrose solutions was 6000 mPa·s (cps). While the emulsion prepared with the 10% sucrose solution became relatively unstable over extended periods of time and temperatures, the emulsion prepared with 30%, for example, remained relatively stable for more than 14-days with respect to viscosity at 4°C, room temperature, and 65°C.
TABLE 4 Properties of emulsions prepared with thermally altered lecithin as a function of sucrose concentration in the discontinuous phase. Sucrose concentration (%) Discontinuousa Phase Holding Capacity (g) Viscosity mPa·s (cps)b 24h 48h 336h 4°C RT 65°C 4°C RT 65°C 10 119 4000 Bc 4000 B B 2000d B 20 113 - - - - - - 30 137 6000 6000 5000 6000 4000 4000 6000d 40 143 6000 - - - - - - a Emulsions prepared with 6 grams (0.3g/5.7g) emulsifier/oil, otherwise emulsions were prepared with 12 grams (0.6g/11.4g) emulsifier oil and 173 grams discontinuous phase for the 10% sucrose solution and 185 grams discontinuous phase for the 30% and 40% sucrose solutions. b Time of measurement after emulsion preparation c B = Broken emulsion d Water droplets appearing on surface. - In this example, lecithin was thermally altered in situ (while dissolved in oil) and the holding capacity of the continuous phase was determined as a function of lecithin originally placed into the oil prior to thermalization. Unaltered lecithin (1.25 g, 2.5 g, 3.75 g, and 5.0 g) was dissolved in 23.75 grams of oil and heated at 180°C for 60 minutes. Corresponding solutions with unaltered lecithin were used for comparison. The results of the comparisons are reported in Table 5 below, from which it can be seen that the holding capacity of the continuous phases containing thermally altered lecithin in accordance with the present invention increase progressively over the corresponding phases containing unaltered lecithin as a function of increasing emulsifier concentration, the increase being from about 15% to 152%.
TABLE 5 Discontinuous phase holding capacities of continuous phases containing lecithin thermalized directly in oil, or unaltered lecithin.a Emulsifier (g/23.75g oil) Holding Capacity (g) TL>L (%) Lb TL 1.25 119 137 15 2.50 95 143 51 3.75 90 185 106 5.0 95 239 152 a Discontinuous phase was a 40% sucrose solution and 6 grams of continuous phase were used for emulsion preparation. b Unstable emulsions. - In this example, emulsion stability was measured as resistance to phase separation with increasing centrifugal force at a constant time and upon standing with time and temperature. For the purpose of this illustration, phase separation refers to the non-random distribution of the particles (cells) containing the aqueous solution in the continuous phase, i.e., settling under the force of gravity. The emulsions are referred to as "broken" when the particles either coalesce forming larger particles or rupture whereby pockets of aqueous phase form within the emulsion and can be separated by centrifugation. In addition, a decrease in viscosity with time was also used as a measure of deterioration in stability. Stability as a function of pH was also determined.
- The measured stabilities of various emulsions made from lecithin prepared as a function of temperature and time of exposure to 180°C as measured by phase separation are given in Table 6 below. After 6-days of standing at 22-23°C, the emulsions prepared using thermally altered lecithin exhibited good stability.
- Emulsions prepared with unaltered lecithin at various emulsifier/oil concentrations were generally unstable and exhibited complete or partial phase separation and breakdown within 24 hours of preparation. The best emulsion prepared with unaltered lecithin contained 4.5 grams emulsifier and 7.5 grams of oil. This creamy-yellow emulsion was stable for 48 hours but thereafter began to show phase separation and breakdown. Upon centrifugation of this emulsion at 2000 rpm for 10 minutes soon after preparation, some water settled to the bottom of the tube and oil rose to the top.
- This example was directed to the effect of pH condition on the emulsions of the subject invention. Emulsions were prepared using 6 grams of thermally altered lecithin/oil (0.3/5.7) and a 40% sucrose solution adjusted to the desired pH (1 to 11) with either HCl or NaOH as the discontinuous phase. Various properties of the emulsions were then determined, which are reported in Table 7 below.
- Good stable emulsions were formed with the discontinuous phase having pH values at 1 to 9. No emulsion was formed at pH 11. There was very little variation in the holding capacity of the emulsions as a function of pH in the 1 to 7 range, although a pH less than 5 was slightly more favorable in this regard. The emulsion prepared at pH 9 held 29% less discontinuous phase than that prepared at pH 7.
TABLE 7 Effects of pH on properties of emulsions prepared with thermally altered lecithin (TL)a Emulsions pH Discontinuous Phase Holding Capacity (g) Viscosity mPa·s (cps) Water lossb (mg) 1 149 - - 3 149 6000 344 5 143 6000 325 7 143 6000 358 9 101 6000 358 11 No emulsion - - a Emulsions prepared with 6g continuous phase (0.3g TL and 5.7g Klearol) and 40% (w/v) sucrose solution as the discontinuous phase. pH was adjusted with HCl or NaOH. b Water loss in a desiccating environment for 20 hours. - Emulsions were prepared using varying amounts of continuous phase, discontinuous phase and emulsifier/oil ratios. Both thermally altered lecithin and unaltered lecithin were employed as emulsifiers, as indicated in Table 8 below. The viscosity and permeability of the various emulsions were determined. The results are reported in Table 8 below.
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-
- The four emulsions prepared in Example 9 were tested for viscosity after being subjected to different temperatures. Viscosity measurements were made after 48 hours and after 14 days. The results are reported in Table 10 below. The results indicate that the emulsions remained remarkably stable with respect to viscosity for more than 14 days, regardless of temperature.
TABLE 10 Effects of temperatures on the viscosity of emulsions prepared with thermally altered lecithin.(d) Temperature(c) (°C) GE1 GE2 GE3 GE4 (a) (b) (a) (b) (a) (b) (a) (b) 4 6000 5000 17000 18000 40000 48000 81000 98000 22-23 6000 5000 17000 19000 37000 47000 89000 97000 65 6000 8000 17000 16000 39000 47000 62000 61000 (a) Measurement made 48 hours after emulsion preparation. (b) Measurements made 336 hours (14 days) after emulsion preparation. (c) Emulsions were placed at the respective temperatures within a few hours after preparation. After 24 hours, the emulsions were allowed to come to room temperature (22-23°C) prior to taking viscosity measurements. The emulsions were left at room temperature thereafter during the 14 day measurement period. (d) See Table 9 for GE emulsion designations - Various emulsions were prepared with 6 grams of a continuous phase containing 0.3 g thermally altered lecithin and 5.7 g Klearol, and a discontinuous phase containing either 5% or 15% glycine at pH values of 4, 7, and 9 for each concentration. The holding capacity, viscosity and water loss after 24 hours was then measured for each of the various emulsions. The results are reported in Table 11 below.
- For the purpose of this example, an emulsion was prepared with thermally altered lecithin/oil (0.3 g/5.7 g) as the continuous phase and 10% NaCl as the discontinuous phase. The holding capacity of this continuous phase was 113 grams, and the viscosity of such an emulsion prepared with 101.4 grams of 10% NaCl solution was 13,000 mPa·s (cps).
- The properties of emulsions prepared with thermally altered lecithin and discontinuous phases containing either 5%, 10% or 20% NaCl solutions were also observed. The holding capacity increased 45% over the NaCl concentration range, and the viscosity increased from 3000 to 14000 mPa·s (cps), or 4.7-fold. These results are reported in Table 12 below.
TABLE 12 Properties of emulsions prepared with thermally altered lecithin and sodium chloride as the solute of the discontinuous phasea. NaCl (%) Discontinuous Phase Holding Capacity (g) Viscosity mPa·s (cps) 5 90 3000 10 119 11000 20 131 14000 a Emulsions were prepared with 6 grams of continuous phase (0.3/5.7, emulsifier/oil). - The weight loss of lecithin at 180°C for various heating times was measured. Beginning with 25 grams of lecithin, 1.5 to 3.5% of the original weight of the lecithin was progressively lost during heating at 180°C for 30 to 480 minutes. Most of the weight reduction would be expected to be due to the loss of water, but a small amount of the material would also be expected to be volatile organic substances produced during thermalization. The results are reported in Table 13 below.
TABLE 13 Weight loss during the thermalization of lecithin as a function of time.a Lecithin (g) Heating Time (min.) Loss Wt. (g) Percentage of Wt. Loss 25 15 0 0 25 30 0.37 1.5 25 60 0.52 2.1 25 90 0.63 2.5 25 120 0.68 2.7 25 240 0.87 3.5 25 480 0.93 3.7 100 90 2.60 2.6 a Thermalization at 180°C. - Various lecithin samples were heated for 60 minutes at a selected temperature. The change in acetone precipitable content was then measured, with the results being reported in Table 14 below.
TABLE 14 Acetone precipitable contents of lecithin as a function of thermalization temperature.a Temperature (°C) Sample Weight Acetone Precipitate Percent of Total 100 229.5 219.3 95.6 125 219.8 178.9 81.3 150 236.0 147.4 62.5 175 196.5 80.3 40.9 200 282.5 86.3 30.6 225 263.3 90.4 34.4 250 295.2 100.9 34.2 a Heated for 60 minutes at the respective temperatures. - Acetone precipitable substances (phosphatides) comprised about 95% percent of the granular lecithin (Centrolex P, Central Soya, Decatur, Indiana) used. Thermalization up to 200°C resulted in a 68% reduction in acetone precipitable substances, and the content of these substances remained relatively constant at 31 to 34% of the total weight of the thermally altered lecithin thereafter up to 250°C. Between 30 and 60 minutes were required to achieve maximum reduction of the acetone precipitable substances when the lecithin was heated at 180°C, and the content of these substances remained relatively constant thereafter up to 480 minutes exposure to this temperature.
- Various samples of lecithin were heated at 180°C for differing lengths of time. The acetone precipitable contents of the heated sample was then measured. The results are reported in Table 15 below.
TABLE 15 Acetone precipitable contents of lecithin as a function of thermalization time.a Time (min.) Sample Weight (mg) Acetone Precipitate (mg) Percent (%) 15 199.6 183.2 91.8 30 203.6 143.6 70.5 60 202.0 64.5 31.9 90 390.4 112.5 28.8 120 299.9 90.7 30.2 240 217.9 60.1 27.6 480 350.2 108.2 30.9 a Heated at 180°C for respective times. - All of the phosphatides in the acetone precipitable fraction of the lecithin were reduced by thermalization as described in the Table above, but essentially all of the non-choline phosphatides were degraded and thus eliminated from the product. The phosphatidylcholine was also reduced considerably.
- The neutral fraction of the thermally altered lecithin contained mainly triacylglycerols, free fatty acids, and two classes of substances unidentified.
- The fatty acid composition of phosphatidylcholine isolated from thermally altered lecithin and unaltered lecithin was compared. It was found that there was an overall increase in the degree of saturation associated with the thermally altered product as shown by a doubling of the relative contents of palmitic and stearic acids, and to the elimination of the most unsaturated component of the phosphatidylcholine molecule, linolenic acid, and reduction by half of linoleic acid. These results are shown in Table 16 below.
TABLE 16 Fatty acid composition of phosphatidylcholine from lecithin before and after thermalization.a Fatty Acid Lecithin Relative Percent (%) Unaltered Lecithin Thermally Altered Palmitic 21.3 42.2 Stearic 5.7 13.9 Oleic 8.0 17.2 Linoleic 58.5 26.6 Linolenic 6.5 - a Thermalization for 90 min at 180°C. - An emulsion was prepared with a thermally altered lecithin/oil ratio of 3 g/5 g as the continuous phase, and 188.2 grams of an 80% ammonium nitrate solution containing 2 grams urea and 1.2 grams triethanolamine as the discontinuous phase. The objective of this example was to demonstrate that an aqueous solution of a very high salt concentration can be effectively emulsified using thermally altered lecithin as the emulsifier into a highly stable emulsion. The resulting emulsion was found very stable in that there was no phase separation and no crystallization of the ammonium nitrate within the supersaturated discontinuous phase for over three months after preparation. The emulsion prepared had a viscosity of 56,000 mPa·s (cps).
- The rates of water loss from emulsions prepared with a continuous phase containing different thermally altered lecithin/oil ratios during the first 48 hours in the desiccating environment described in Example 8 was explored in this Example. It was found that the rate of water loss was essentially the same for emulsions with ratios of 0.6/11.4 and 1.2/10.75, but the rates decreased progressively with increasing thermally altered lecithin contents of 2.5/9.5 and 4.5/7.5. However, after 144 hours, the amount of water lost in the three emulsions having the lowest emulsifier/oil ratios was essentially the same, and it would be expected that after an additional 48 to 72 hours all of the above emulsions would have lost the same amount of water. Generally, water loss from the emulsion was inversely related to the concentration of the solution in the discontinuous phase.
- A comparative emulsion was prepared with unaltered lecithin in an emulsifier/oil ratio of 4.5/7.5. The emulsion had a viscosity of 15,000 mPa·s (cps). The viscosity of this emulsion dropped with time at room temperature to 9,000 mPa·s (cps) at 48 hours, 4,000 mPa·s (cps) at 72 hours and 3,000 mPa·s (cps) at 96 hours, which indicated a progressive deterioration with time.
- Emulsions were prepared using a constant (0.3 g) amount of thermally altered lecithin and varying oil (Klearol) contents, and 40% sucrose as the discontinuous phase, to determine the effect of oil content on emulsion formation and the stability of such emulsions. The results are reported in Table 17 below.
- The holding capacity of the continuous phases increased progressively with increasing oil content from 150 g at 6 g of oil to 360 g at 20 g of oil which is a 140% increase in holding capacity. The emulsion having the lowest oil content had the highest viscosity at 6000 mPa·s (cps), and that of the emulsion containing 9 g oil was 4000 mPa·s (cps). The viscosity of emulsions containing 12 to 20 g of oil was 2000 mPa·s (cps).
- The emulsion containing only 6 g of oil lost the greatest amount of water 4 days after preparation but 2 days in the dessiccating environment, whereas water loss from the other emulsions was relatively constant. The emulsions containing 6 and 9 g of oil remained stable for at least 18 days after preparation, but the ones with higher oil contents showed phase separation after 6 days and had decomposed after 14 days.
Claims (16)
- A water-in-oil emulsion comprised of(i) a continuous oil phase,(ii) a discontinuous aqueous phase, and(iii) an emulsion stabilizing amount of a thermally altered lecithin composition which has been prepared by heating lecithin at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes.
- A water-in-oil emulsion according to claim 1, wherein the thermally altered lecithin has been prepared by heating at a temperature in the range of from 160°C to 200°C, preferably from 175°C to 185°C.
- A water-in-oil emulsion according to claim 1 or 2, wherein the thermally altered lecithin has been prepared by heating for a period of time ranging from 60 to 480 minutes, preferably from 60 to 120 minutes.
- A water-in-oil emulsion according to claim 1, 2 or 3, wherein the continuous oil phase comprises from 1.5 to 6.0 percent by weight of the total emulsion composition, preferably from 1.8 to 5.5 weight percent of the total emulsion composition.
- A water-in-oil emulsion according to any one of the preceding claims, wherein tee thermally altered lecithin composition comprises from 0.05 to 2.5 weight percent of the total emulsion composition, preferably from 0.08 to 2.2 weight percent of the total emulsion composition.
- A water-in-oil emulsion according to any one of the preceding claims, wherein the weight ratio of thermally altered lecithin composition to continuous oil phase ranges from 0.5/11.5 to 1, preferably from 0.6/11.4 to 4.8/7.2.
- A water-in-oil emulsion according to any one of the preceding claims, wherein the pH of the discontinuous aqueous phase ranges from 1 to 9, preferably from 1 to 7, especially from 1 to 5.
- A water-in-oil emulsion according to any one of the preceding claims, wherein the discontinuous aqueous phase is comprised of an amino acid, a carbohydrate or a salt.
- A water-in-oil emulsion according to claim 8, wherein the discontinuous aqueous phase is comprised of glycine, sucrose, sodium chloride or ammonium nitrate.
- A water-in-oil emulsion according to any one of the preceding claims, wherein the thermally altered lecithin is prepared from soybean lecithin.
- A process for preparing a water-in-oil emulsion as defined in claim 1, which process comprises the steps of(i) heating lecithin at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes,(ii) mixing the product of (i) with an oil, and(iii) adding to the product of (ii) an aqueous phase with agitation to thereby yield a water-in-oil emulsion.
- A process according to claim 11, wherein the lecithin is heated at a temperature in the range of from 160°C to 200°C, preferably from 175°C to 185°C.
- A process according to claim 11 or 12, wherein the lecithin is heated for a period of time ranging from 60 to 480 minutes, preferably from 60 to 120 minutes.
- A process for preparing a water-in-oil emulsion as defined in claim 1, which process comprises the steps of(i) heating lecithin in an oil at a temperature in the range of from 100°C to 250°C for a period of time ranging from 15 to 480 minutes, and(ii) adding to the product of (i) an aqueous phase with agitation to thereby yield a water-in-oil emulsion.
- A process according to claim 14, wherein the product of step (i) is first allowed to cool to a temperature below 100°C before the aqueous phase is added thereto.
- Use of a thermally altered lecithin composition which has been prepared in the manner defined in claim 1 as an emulsifier in a water-in-oil emulsion.
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BR (1) | BR8907350A (en) |
CA (1) | CA1337109C (en) |
DE (1) | DE68912583T2 (en) |
WO (1) | WO1989009745A1 (en) |
ZA (1) | ZA892472B (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2043279T3 (en) * | 1989-06-07 | 1993-12-16 | Kao Corp | EDIBLE EMULSION OF OIL IN WATER. |
US5041293A (en) * | 1989-12-28 | 1991-08-20 | Wm. Wrigley Jr. Company | Method of adding lecithin to chewing gum |
US5834539A (en) * | 1991-10-15 | 1998-11-10 | Krivohlavek; Dennis | Multiple phase emulsions in burner fuel, combustion, emulsion and explosives applications |
SE507450C2 (en) * | 1991-12-20 | 1998-06-08 | Karlshamns Oils & Fats Ab | Heat-resistant chocolate composition and process for making it |
US5431719A (en) * | 1992-10-28 | 1995-07-11 | Creative Products Inc. Of Rossville | Non-aerosol foodstuffs parting composition |
US5296021A (en) * | 1992-10-28 | 1994-03-22 | Creative Products Inc. Of Rossville | Aerosol-dispensable foodstuffs parting composition |
NL9400757A (en) * | 1994-05-06 | 1995-12-01 | Campina Melkunie Bv | Heat-stable oil-in-water emulsions stabilized by hydrolysates. |
US5525361A (en) * | 1995-03-16 | 1996-06-11 | Wm. Wrigley Jr. Company | Color stable chewing gum bases and chewing gums made therefrom |
US6113970A (en) * | 1997-02-03 | 2000-09-05 | Lipton, Division Of Conopco, Inc. | Lecithin based spray product |
FR2766737B1 (en) * | 1997-07-31 | 1999-09-24 | Centre Nat Rech Scient | MULTIPLE EMULSIONS AND THEIR APPLICATIONS |
US5980919A (en) * | 1997-11-10 | 1999-11-09 | Potlatch Corporation | Emollient compositions and methods of application to a substrate by electrostatic spraying |
UA73327C2 (en) * | 1999-11-15 | 2005-07-15 | Water and oil emulsion | |
US6890548B1 (en) * | 2002-05-14 | 2005-05-10 | Robt Morgan, Inc. | Rumen bypass supplement |
BRPI0414500A (en) * | 2003-09-19 | 2006-11-07 | Drugtech Corp | pharmaceutical formulation composition to treat a vaginal infection, and methods to treat a vaginal infection, to stabilize a clindamycin formulation, to treat or prevent a recurrence of a vaginal infection in a patient and to treat vaginal conditions |
US20060057172A1 (en) | 2004-09-13 | 2006-03-16 | Anderson David L | Liquid animal repellant containing oils of black pepper and capsicum |
US7147634B2 (en) | 2005-05-12 | 2006-12-12 | Orion Industries, Ltd. | Electrosurgical electrode and method of manufacturing same |
US8814861B2 (en) | 2005-05-12 | 2014-08-26 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
EA200870153A1 (en) * | 2006-01-05 | 2008-12-30 | Драгтек Корпорейшн | COMPOSITION AND METHOD OF ITS USE |
JP4551944B2 (en) * | 2007-05-15 | 2010-09-29 | 利春 深井 | Oil emulsion |
US9193898B2 (en) | 2011-06-08 | 2015-11-24 | Nalco Company | Environmentally friendly dispersion system used in the preparation of inverse emulsion polymers |
CA2899267C (en) * | 2013-01-31 | 2016-09-06 | Unilever Plc | Process for the manufacture of edible water-in-oil emulsions |
KR102644391B1 (en) * | 2018-11-29 | 2024-03-07 | (주)아모레퍼시픽 | Cosmetic composition of water-in-oil type having improved stability |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US2193873A (en) * | 1937-05-14 | 1940-03-19 | Jordan Stroud | Water dispersible lecithin |
US2223558A (en) * | 1938-03-05 | 1940-12-03 | Albert K Epstein | Emulsion |
US2299743A (en) * | 1941-05-12 | 1942-10-27 | Albert K Epstein | Composition of matter |
US2552706A (en) * | 1946-03-08 | 1951-05-15 | Fredrik Andre Moller | Emulsifying agent, method of making said emulsifying agent, and waterin-oil emulsion using said emulsifying agent |
US2577218A (en) * | 1946-12-19 | 1951-12-04 | Shell Dev | Emulsions |
US2678320A (en) * | 1949-02-25 | 1954-05-11 | American Lecithin Company Inc | Phosphatide preparations |
US2907777A (en) * | 1957-04-26 | 1959-10-06 | Glidden Co | Hydrogenated lecithin and process for preparing same |
NL242560A (en) * | 1959-08-21 | |||
US3026341A (en) * | 1959-12-21 | 1962-03-20 | Central Soya Co | Process for the hydrogenation of phosphatides |
US3318704A (en) * | 1965-10-22 | 1967-05-09 | American Lecithin Co | Compositions with fatty oil and safflower phosphatide |
DE1692566A1 (en) * | 1967-04-18 | 1971-08-05 | Unilever Nv | Process for the production of partially hydrolyzed plant phosphatides with an improved emulsifying effect |
US3962292A (en) * | 1974-07-29 | 1976-06-08 | Central Soya Company, Inc. | Phosphatide preparation process |
US4330422A (en) * | 1977-02-01 | 1982-05-18 | Minnesota Mining And Manufacturing Company | Treating composition containing white oil |
JPS54107530A (en) * | 1978-02-10 | 1979-08-23 | Hohnen Oil | Prevention of heat browning of phospholipid |
JPS54112825A (en) * | 1978-02-22 | 1979-09-04 | Hohnen Oil Co Ltd | Prevention of heat browning of phospholipids |
JPS54124009A (en) * | 1978-03-22 | 1979-09-26 | Hohnen Oil Co Ltd | Suppression of heat browning of phospholipids |
US4400295A (en) * | 1979-03-24 | 1983-08-23 | Loire Cosmetics Co., Ltd. | Emulsifier composition |
JPS59157193A (en) * | 1983-02-25 | 1984-09-06 | 長浜 章 | Manufacture of oil containing lecithin |
-
1988
- 1988-04-04 US US07/177,956 patent/US4943389A/en not_active Expired - Lifetime
-
1989
- 1989-04-03 BR BR898907350A patent/BR8907350A/en not_active IP Right Cessation
- 1989-04-03 DE DE68912583T patent/DE68912583T2/en not_active Expired - Fee Related
- 1989-04-03 AU AU34217/89A patent/AU631352B2/en not_active Ceased
- 1989-04-03 JP JP1504366A patent/JPH04500301A/en active Pending
- 1989-04-03 EP EP89904684A patent/EP0408642B1/en not_active Expired - Lifetime
- 1989-04-03 CA CA000595541A patent/CA1337109C/en not_active Expired - Lifetime
- 1989-04-03 WO PCT/US1989/001342 patent/WO1989009745A1/en active IP Right Grant
- 1989-04-04 ZA ZA892472A patent/ZA892472B/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP0408642A4 (en) | 1991-03-13 |
AU3421789A (en) | 1989-11-03 |
AU631352B2 (en) | 1992-11-26 |
WO1989009745A1 (en) | 1989-10-19 |
DE68912583T2 (en) | 1994-06-01 |
ZA892472B (en) | 1990-03-28 |
CA1337109C (en) | 1995-09-26 |
BR8907350A (en) | 1991-03-19 |
JPH04500301A (en) | 1992-01-23 |
EP0408642A1 (en) | 1991-01-23 |
DE68912583D1 (en) | 1994-03-03 |
US4943389A (en) | 1990-07-24 |
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